Anthraquinone vat dyestuffs



United States Patent 2,705,718 ANTHRAQUINONE VAT DYESTUFFS EduardMoergeli, Neuewelt, near Basel, Switzerland, assignor to Ciba Limited,Basel, Switzerland, a Swiss firm N0 Drawing. Application December 17,1951, Serial No. 262,173

Claims priority, application Switzerland July 1, 1948 6 Claims. (Cl.260-368) latter being selected from the group consisting of 1-.

amino (2 fluorobenzoylamino)-anthraquinone, 1- amino 5 (4'-chloro 2'fiuorobenzoylamino)-anthraquinone and l-amino 5 (5' -chloro 2fluorobenzoylamino) -anthraquinone.

"Accordingly the new dyestuffs correspond to the for mula i) HNOCXQCO NHwherein X2 stands for an aromatic carbocyclic radical and each R standsfor a member selected from the group consisting of the radicalscorresponding to the and 1-amino-5-(4'- or5-chloro-2'-fluorobenzoylamino)-anthraquinone can be prepared bymonoacylation of 1:S-d i aminoanthraquinone. The 2-fluoro-4.- or-5-chlorobenzo1c acid which are necessary for introducing thecorresponding acyl radicals can be made by methods in themselves known.A suitable method for preparing such compounds consists, for example, indiazotizing 1-amino-2-methyl-4- or -5-chlorobenzene with the aid ofhydrofluoric acid and sodium nitrite, the appropriate fluorinesubstitution prodnot being formed either simultaneously withdiazotization by the action of the hydrofluoric acid or by subsequentconversion of the diazo compound into the fluorine substitution productwith the splitting oil of nitrogen. In the resultingl-fiuoro-Z-methyl-4- or -5-.chlorobenzene the methyl group is eitheroxidized directly to .a carboxylic acid group or converted itno atrichloromethyl group followed by hydrolysis of the latter to acarboxylic acid group.

The 1-amino-5-(2-fiuorobenzoylamino)-anthraquinone orl-amino-5-(2'-fluoro-4'- or -5-chlorobenzoylamino)- anthraquinone isacylated with acylating agents derived from aromatic dicarboxylic acidswhich may contain up to four aromatic six-membered condensed or noncondensed rings such as isoand terephthalic acid, naphthalene-Z6-dicarboxylic acid, dip'henyl-4 4'-dicarboxylic acid, or fiuoranthenedicarboxylic acid.

In all cases it is of advantage to carry out the acylation with the aidof reactive derivatives of the carboxylic acids in question. Thereaction may be conducted in a solvent or dispersing medium,advantageously of high boiling point such 351110110, diortrichlorobenzene, nitrobenzene or naphthalene at a raised temperature,for example, within the range from about .100 C. to the boiling point ofthe solvent or dispersing medium used.

The products of the invention are valuable vat dyestuffs. They can beused in known manner as such or in the form of their leuco-ester saltsobtainable by known methods for dyeing and printing a very wide varietyof fibers of animal and especially vegetable character, thus wool andsilk, but especially cotton, linen, and artificial silk or staple fibersof regenerated cellulose and also superpolyamide fibers.

The following examples illustrate the invention the parts andpercentages being by weight unless otherwise stated and the relationshipof parts by weight to parts bly Yolume being the same as that of thekilogram to t e'iter:

Example 1 /2 hour with stirring to 140 C. and then for so long at190-200 C. that the formation of the dyestutf of the formula iscomplete. The dyestutf is then worked up and if necessary subjected to apurification with hypochlorite solution. It dyes the fiber from aBordeaux colored hydrosulphite vatin pure yellow fast shades and isdistinguished in printing also by clarity and strength.

A dyestuif with very similar properties is obtained when instead ofisophthalic acid dichloride the same quantity of terephthalic aciddichloride is employed.

The l-amino 5 (ortho-fluorobenzoylamino)-anthraquinone employed can beobtained by partial acylation of 1:S-diamino-anthraquinone withortho-fluorobenzoyl chloride or froml-chloro-5-(ortho-fluorobenzoylamino)- anthraquinone by replacement ofthe chlorine atom by the toluene sulphonamide residue and splitting offof the sulphonic acid residue. It crystallizes from pyridine ornitrobenzene in fine red crystals which melt at 26.9.5270 C.(uncorrected).

Example 2 3.27 parts of fluoranthene dicarboxylic acid dichloride of thecomposition set out in Patent No. 2,299,826, and 7.2 parts ofi-an1ino-5-(ortho-fiuorooenzoylamino)wanthraquinone are stirred for 3hours at 210 C. in 250 parts by volume of trichlorobenzene. The dyestuffformed is then filtered with suction at (C. and worked up in thecustomary manner. it constitutes a brown yellow powder and dissolves inconcentrated sulphuric acid with brown color. For purification 5 partsof dye stufi in fine aqueous suspension are oxidized at 95-l00 C. with20 parts by volume of 13 per cent sodiumnhypochlorite solution. Thepurified dyestufi dyes cotton from a Bordeaux colored vat in full yellowshades of very good wet fastness properties.

Example 3 A mixture of 4 parts of l-amino-5-(2'-flu:oro-4-chloro-(boiling at 103104 benzoylamino)-anthraquinone, 1 part of terephthalicacid dichloride and 150 parts of trichlorobenzene is heated at the boilfor 2 hours while stirring. The whole is allowed to cool to 120 C. andthe dyestuff of the formula is separated by filtration. It dyes cottonfrom a Bordeaux colored vat fast pure yellow tints.

, When instead of terephthalic acid dichloride an equivalent quantity ofacid chloride of the 4-fiuorisophthalic acid is used, a dyestuif withsimilar tinctorial properties is ob tained. I

The l-amino-S-(4-chloro-2-fluorobenzoylamino) anisseparated byfiltration. Itdissolves in concentratedsul furic acid with an orange redcoloration and dyes cotton fast yellow tints.

By methods exactly analogous to those described in the NH-CO- foregoingexamples there can be obtained from, two molecular proportions of thel-amino 5 acylaminoanthraquinone given in column I of the followingtable and 1 mo lecular proportion of the adjacent dicarboxylic acid incolumn II, further dyestuffs having the properties given in columns IIIand IV. The dicarboxylic acid is advantageously used in the form of thedichloride.

I II III IV Anthrequinone component. 2 Dyeing on Color the mom Acidcomponent, 1 mol cotton hydr ogttflfite 1 l-amino (2-fluoro-4chlorolsophthallc acid pure yellow B o r d e a u-x benzoylamluo)anthraquired. none. 2 1-amlno-4- (2'-fluoro-5'-chloro- .do .-do Do.

benzoylamino) anthraqulnone. 3.. do terephthalic acid do reddish blue. 4dlphieinyl 4:4 dlcarboxyllc full yellow- Bordeaux.

thraquinone used (melting point 279 C.) can be made by Example 5 thepartial acylation of 1:5-diaminoanthraquin0ne with 2-fluoro-4-chlorobenzoyl chloride, or from 1-chloro-5-(4-chloro-2-fluorobenzoylamino)anthraquinone by replacing the chlorine atomby a toluene sulfonamide radical followed by splitting oil of thesulfonic acid radical. .1-

fiuorobenzoylamino) anthraamino-S (5-chloro 2 in the same quinone(melting point 269 C.) can be made manner.

'2 fiuoro-4-chlorobenzoyl chloride (boiling at 105106 C. under 14 mm.pressure) can be made from 2-fluoro-4- chlorobenzoic acid (melting point205 C.) by reaction with thionyl chloride. The 2-fluoro-4-chlorobenzoicacid can advantageously be prepared by the oxidation with potassiumpermanganate of 2-fiuoro-4-chlorotoluene (boiling at 158 C. under 743mm. pressure), which latter can be obtained fromZ-amino-4-chloro-toluene by the hydrofluoboric acid method of Balz andSchiemann (Berichte der deutschen Chemischen Gesellschaft, vol. 60, page1188 (1927)) in excellent yield. In an analogous manner2-fiuoro-5-chlorobenzoyl chloride C. under 15 mm. pressure) can beobtained from 2-amino-5-chloro-toluene by way of the intermediateproducts 2-fiuoro-5-chloro-toluene (boiling at 156 C. under 741 mm.pressure) and Z-fluoro-S-chlorobenzoic acid (melting at 149-150 C.).

Example 4 A mixture of 0.89 part of diphenyl-4:4'-dicarboxylic acid, 6parts of thionyl chloride, 0.05 part of pyridine and 90'par'ts oftrichlorobenzene is stirred for minutes at 80 C. and for a further 30minutes at 120 C., and is then heated at the boil, whereupon thionylchloride and some of the solvent distil 0E. The solution is allowed to 1part of the dyestulf obtained according to the first paragraph ofExample 1 is vatted at C. in parts of water with addition of 2 parts ofsodium hydrosulfite and --4 parts by volume of caustic soda solution of36 B. The

stock vat thus obtained is added to a solution of 2 parts of sodiumhydrosulfite and 4 parts by volume of caustic soda solution of 36 B. in2000 parts of water. In the dyebath .thus obtained 100v parts of cottonare dyed for 1 hour at cool to 100 C., 3 parts of1-amino-5-(2-fluoro-4-chlorobenzoylamino)-anthraquinone are added, andthe whole is heated for 2 hours at ZOO-210 C. After cooling to about C.the dyestuff of the formula CIQCO-HN and 40-50 C. with addition of 10parts of sodium chloride. The cotton is thereupon squeezed out, oxidizedin the air,

rinsed, acidified, rinsed again and soaped at the boil. It

becomesdyed in pure yellow shades.

What is claimed is: 1. An anthraquinone vat dystufi of the formulaR-0C-NH 3' NH-oo-R of the radicals corresponding to the formulae 2. Ananthraquinone vat dyestutf of the formula a-oc-NH o o HN-GO-R wherein X:stands for an aromatic carbocyclic radical and 10 each R stands for amember selected from the group consisting of the radicals correspondingto the formulae and 3. An anthraquinone vat dyestulf containing at themost wherein X3 stands for an aromatic carbocyclic radical and the -CO-groups are bound directly to aromatic ring carbon atoms of X3.

An anthraquinone vat dyestuff containing at the most three halogen atomsper anthraquinone radical and corresponding to the formula OHN-OC-Xz-CO-NH 0 5. The anthraquinone vat dyestuff of the formula threehalogen atoms per anthraquinone radical and corresponding to the formula6. The anthraquinone vat dyestufl of the formula References Cited in thetile of this patent UNITED STATES PATENTS May 11, 1948 July 10, 1951OTHER REFERENCES Elseviers Encyclopedia of Organic Chemistry, Series-Carboisocyclic Condensed Compounds-lB-Tricyclic Compounds, pp. 465-466,1946.

1. AN ANTHRAQUINONE VAT DYSTUFF OF THE FORMULA